SCIENCE CHINA Materials, Volume 63 , Issue 12 : 2570-2581(2020) https://doi.org/10.1007/s40843-020-1335-x

High-performance polyamide nanofiltration membrane with arch-bridge structure on a highly hydrated cellulose nanofiber support

More info
  • ReceivedApr 1, 2020
  • AcceptedApr 4, 2020
  • PublishedMay 18, 2020


Funded by

the National Natural Science Funds for Distinguished Young Scholar(51625306)

the Key Project of National Natural Science Foundation of China(21433012)

the National Natural Science Foundation of China(51603229,21406258)

the State Key Laboratory of Separation Membranes and Membrane Processes(Tianjin,Polytechnic,University,No.,M1-201801)

and the CAS Pioneer Hundred Talents Program.


This work was supported by the National Natural Science Funds for Distinguished Young Scholar (51625306), the Key Project of the National Natural Science Foundation of China (21433012), the National Natural Science Foundation of China (51603229, 21406258), and the State Key Laboratory of Separation Membranes and Membrane Processes (Tianjin Polytechnic University, No. M1-201801). Funding support from the CAS Pioneer Hundred Talents Program is grateful appreciated as well.

Interest statement

The authors declare that they have no conflict of interest.

Contributions statement

Zhu Y and Jin J designed the experiments and developed the theory; Teng X performed the experiments; Lin H performed the measurement of SFG; Liu S contributed to the MD analysis; Teng X, Liang Y, Wang Z, Fang W and Zhu Y performed the data analysis; Teng X and Zhu Y wrote the paper with support from Jin J and Lin S; all authors contributed to the general discussion.

Author information

Jian Jin received her BSc (1996) and PhD degrees (2001) from Jilin University of China. She then worked as a JSPS (Japan Society for the Promotion of Science) postdoctoral fellow in the Research Center of Advanced Science and Technology at Tokyo University, Japan. From 2004 to 2009, she worked as a senior researcher at the National Institute for Materials Science, Japan, under Dr. Izumi Ichinose. In 2009, she joined Suzhou Institute of Nano-Tech and Nano-Bionics (SINANO) at the Chinese Academy of Sciences (CAS) as a group leader. Her research interests include the design of advanced filtration membranes for environmental applications.

Yuzhang Zhu received his BSc degree (2009) from Anhui University of Science and Technology and completed his PhD (2015) from the University of Chinese Academy of Sciences. He then worked as a postdoctoral fellow in Professor Jian Jin’s group at SINANO, CAS. From 2017, he joined SINANO as an associate research professor. His current research interests focus on advanced membranes for nanofiltration, oil/water separation and stimuli-responsive separation.

Xiangxiu Teng received her BSc degree from Qingdao University of Science and Technology in 2016. Then, she joined Shanghai University of Science and Technology. At 2017, she started her research program under the supervision of Professor Jian Jin. Her research interest is the preparation of polyamide nanofiltration membrane for desalination.


Supplementary information

Supporting data are available in the online version of the paper.


[1] Gleick PH. Global freshwater resources: soft-path solutions for the 21st century. Science, 2003, 302: 1524-1528 CrossRef PubMed Google Scholar

[2] Mekonnen MM, Hoekstra AY. Four billion people facing severe water scarcity. Sci Adv, 2016, 2: e1500323 CrossRef PubMed Google Scholar

[3] Vörösmarty CJ, Green P, Salisbury J, et al. Global water resources: vulnerability from climate change and population growth. Science, 2000, 289: 284-288 CrossRef PubMed Google Scholar

[4] Elimelech M, Phillip WA. Elimelech M. Google Scholar

[5] Porada S, Zhao R, van der Wal A, et al. Review on the science and technology of water desalination by capacitive deionization. Prog Mater Sci, 2013, 58: 1388-1442 CrossRef Google Scholar

[6] Greenlee LF, Lawler DF, Freeman BD, et al. Reverse osmosis desalination: Water sources, technology, and today’s challenges. Water Res, 2009, 43: 2317-2348 CrossRef PubMed Google Scholar

[7] Werber JR, Osuji CO, Elimelech M. Materials for next-generation desalination and water purification membranes. Nat Rev Mater, 2016, 1: 16018 CrossRef Google Scholar

[8] Paul M, Jons SD. Chemistry and fabrication of polymeric nanofiltration membranes: A review. Polymer, 2016, 103: 417-456 CrossRef Google Scholar

[9] Mohammad AW, Teow YH, Ang WL, et al. Nanofiltration membranes review: Recent advances and future prospects. Desalination, 2015, 356: 226-254 CrossRef Google Scholar

[10] Zhou D, Zhu L, Fu Y, et al. Development of lower cost seawater desalination processes using nanofiltration technologies—A review. Desalination, 2015, 376: 109-116 CrossRef Google Scholar

[11] Park HB, Kamcev J, Robeson LM, et al. Maximizing the right stuff: The trade-off between membrane permeability and selectivity. Science, 2017, 356: eaab0530 CrossRef PubMed Google Scholar

[12] Geise GM, Park HB, Sagle AC, et al. Water permeability and water/salt selectivity tradeoff in polymers for desalination. J Membrane Sci, 2011, 369: 130-138 CrossRef Google Scholar

[13] Hilal N, Al-Zoubi H, Darwish NA, et al. A comprehensive review of nanofiltration membranes: Treatment, pretreatment, modelling, and atomic force microscopy. Desalination, 2004, 170: 281-308 CrossRef Google Scholar

[14] Sorribas S, Gorgojo P, Téllez C, et al. High flux thin film nanocomposite membranes based on metal–organic frameworks for organic solvent nanofiltration. J Am Chem Soc, 2013, 135: 15201-15208 CrossRef PubMed Google Scholar

[15] Yoon K, Hsiao BS, Chu B. High flux nanofiltration membranes based on interfacially polymerized polyamide barrier layer on polyacrylonitrile nanofibrous scaffolds. J Membrane Sci, 2009, 326: 484-492 CrossRef Google Scholar

[16] Choi W, Gu JE, Park SH, et al. Tailor-made polyamide membranes for water desalination. ACS Nano, 2015, 9: 345-355 CrossRef PubMed Google Scholar

[17] Wang JJ, Yang HC, Wu MB, et al. Nanofiltration membranes with cellulose nanocrystals as an interlayer for unprecedented performance. J Mater Chem A, 2017, 5: 16289-16295 CrossRef Google Scholar

[18] Bui NN, McCutcheon JR. Hydrophilic nanofibers as new supports for thin film composite membranes for engineered osmosis. Environ Sci Technol, 2013, 47: 1761-1769 CrossRef Google Scholar

[19] Inukai S, Cruz-Silva R, Ortiz-Medina J, et al. High-performance multi-functional reverse osmosis membranes obtained by carbon nanotube·polyamide nanocomposite. Sci Rep, 2015, 5: 13562 CrossRef PubMed Google Scholar

[20] Zhang Y, Su Y, Peng J, et al. Composite nanofiltration membranes prepared by interfacial polymerization with natural material tannic acid and trimesoyl chloride. J Membrane Sci, 2013, 429: 235-242 CrossRef Google Scholar

[21] Wang C, Li Z, Chen J, et al. Covalent organic framework modified polyamide nanofiltration membrane with enhanced performance for desalination. J Membrane Sci, 2017, 523: 273-281 CrossRef Google Scholar

[22] Zhou Z, Hu Y, Boo C, et al. High-performance thin-film composite membrane with an ultrathin spray-coated carbon nanotube interlayer. Environ Sci Technol Lett, 2018, 5: 243-248 CrossRef Google Scholar

[23] Qian H, Zheng J, Zhang S. Preparation of microporous polyamide networks for carbon dioxide capture and nanofiltration. Polymer, 2013, 54: 557-564 CrossRef Google Scholar

[24] An QF, Sun WD, Zhao Q, et al. Study on a novel nanofiltration membrane prepared by interfacial polymerization with zwitterionic amine monomers. J Membrane Sci, 2013, 431: 171-179 CrossRef Google Scholar

[25] Li Y, He G, Wang S, et al. Recent advances in the fabrication of advanced composite membranes. J Mater Chem A, 2013, 1: 10058-10077 CrossRef Google Scholar

[26] Wang H, Zhang Q, Zhang S. Positively charged nanofiltration membrane formed by interfacial polymerization of 3,3ʹ,5,5ʹ-biphenyl tetraacyl chloride and piperazine on a poly(acrylonitrile) (PAN) support. J Membrane Sci, 2011, 378: 243-249 CrossRef Google Scholar

[27] Zhu Y, Xie W, Gao S, et al. Single-walled carbon nanotube film supported nanofiltration membrane with a nearly 10 nm thick polyamide selective layer for high-flux and high-rejection desalination. Small, 2016, 12: 5034-5041 CrossRef PubMed Google Scholar

[28] Karan S, Jiang Z, Livingston AG. Sub-10 nm polyamide nanofilms with ultrafast solvent transport for molecular separation. Science, 2015, 348: 1347-1351 CrossRef PubMed Google Scholar

[29] Jeong BH, Hoek EMV, Yan Y, et al. Interfacial polymerization of thin film nanocomposites: a new concept for reverse osmosis membranes. J Membrane Sci, 2007, 294: 1-7 CrossRef Google Scholar

[30] Ma H, Burger C, Hsiao BS, et al. Highly permeable polymer membranes containing directed channels for water purification. ACS Macro Lett, 2012, 1: 723-726 CrossRef Google Scholar

[31] Wang Z, Wang Z, Lin S, et al. Nanoparticle-templated nanofiltration membranes for ultrahigh performance desalination. Nat Commun, 2018, 9: 2004 CrossRef PubMed Google Scholar

[32] Tan Z, Chen S, Peng X, et al. Polyamide membranes with nanoscale Turing structures for water purification. Science, 2018, 360: 518-521 CrossRef PubMed Google Scholar

[33] Li X, Wang KY, Helmer B, et al. Thin-film composite membranes and formation mechanism of thin-film layers on hydrophilic cellulose acetate propionate substrates for forward osmosis processes. Ind Eng Chem Res, 2012, 51: 10039-10050 CrossRef Google Scholar

[34] Yin J, Kim ES, Yang J, et al. Fabrication of a novel thin-film nanocomposite (TFN) membrane containing MCM-41 silica nanoparticles (NPs) for water purification. J Membrane Sci, 2012, 423-424: 238-246 CrossRef Google Scholar

[35] Chae HR, Lee J, Lee CH, et al. Graphene oxide-embedded thin-film composite reverse osmosis membrane with high flux, anti-biofouling, and chlorine resistance. J Membrane Sci, 2015, 483: 128-135 CrossRef Google Scholar

[36] Ghosh AK, Hoek EMV. Impacts of support membrane structure and chemistry on polyamide–polysulfone interfacial composite membranes. J Membrane Sci, 2009, 336: 140-148 CrossRef Google Scholar

[37] Chen Y, Liu F, Wang Y, et al. A tight nanofiltration membrane with multi-charged nanofilms for high rejection to concentrated salts. J Membrane Sci, 2017, 537: 407-415 CrossRef Google Scholar

[38] Li L, Zhang S, Zhang X. Preparation and characterization of poly(piperazineamide) composite nanofiltration membrane by interfacial polymerization of 3,3ʹ,5,5ʹ-biphenyl tetraacyl chloride and piperazine. J Membrane Sci, 2009, 335: 133-139 CrossRef Google Scholar

[39] Shen J, Yu C, Ruan H, et al. Preparation and characterization of thin-film nanocomposite membranes embedded with poly(methyl methacrylate) hydrophobic modified multiwalled carbon nanotubes by interfacial polymerization. J Membrane Sci, 2013, 442: 18-26 CrossRef Google Scholar

[40] Leng C, Sun S, Zhang K, et al. Molecular level studies on interfacial hydration of zwitterionic and other antifouling polymers in situ. Acta Biomater, 2016, 40: 6-15 CrossRef PubMed Google Scholar

[41] Leng C, Hung HC, Sieggreen OA, et al. Probing the surface hydration of nonfouling zwitterionic and poly(ethylene glycol) materials with isotopic dilution spectroscopy. J Phys Chem C, 2015, 119: 8775-8780 CrossRef Google Scholar

[42] Nagasawa D, Azuma T, Noguchi H, et al. Role of interfacial water in protein adsorption onto polymer brushes as studied by SFG spectroscopy and QCM. J Phys Chem C, 2015, 119: 17193-17201 CrossRef Google Scholar

[43] Chiu HC, Lin YF, Hung SH. Equilibrium swelling of copolymerized acrylic acid−methacrylated dextran networks:  Effects of pH and neutral salt. Macromolecules, 2002, 35: 5235-5242 CrossRef Google Scholar

[44] Liu H, Zhen M, Wu R. Ionic-strength- and pH-responsive poly[acrylamide-co-(maleic acid)] hydrogel nanofibers. Macromol Chem Phys, 2007, 208: 874-880 CrossRef Google Scholar

[45] de Groot GW, Santonicola MG, Sugihara K, et al. Switching transport through nanopores with pH-responsive polymer brushes for controlled ion permeability. ACS Appl Mater Interfaces, 2013, 5: 1400-1407 CrossRef PubMed Google Scholar

  • Figure 1

    Characterization of BCNs and BCN nanofilm. (a, b) Photographs of bacterial cellulose bulk and BCN dispersion, respectively. (c, d) AFM image of BCNs and corresponding statistic distribution of BCN diameters. (e, f) Top view and cross-sectional SEM images of BCN nanofilm deposited on PTFE MF membrane. (g, h) Photographs of free-standing BCN nanofilm dyed by Direct Red 80.

  • Scheme 1

    Fabrication of arch-bridge TFC PA NF membrane. (a) Schematic of IP of PA on NaCl-reinforced hydrophilic BCN nanofilm. A schematic demonstrating the formation of PA active layer with arch-bridge structure on a support with good water wettability (b) and with spotted structure on a support with poor water wettability (c).

  • Figure 2

    Effect of NaCl on the surface wettability and permeance of BCN nanofilm. (a) Surface wettability of the BCN nanofilm to pure water and water containing 1 wt% NaCl. (b) Permeance variation of the BCN nanofilm as a function of filtration time using pure water and 1 wt% NaCl aqueous solution as feed, respectively. Applied pressure is 1 bar.

  • Figure 3

    Structure characterization of TFC-PA NF membranes. (a) Top view SEM image, (b) AFM image, and (c) cross-sectional TEM image of the NF membrane prepared in PIP aqueous solution without addition of salt. (d) Top view SEM image, (e) AFM image, and (f) TEM image of the cross-sectional membrane prepared in PIP aqueous solution with the addition of 1 wt% NaCl.

  • Figure 4

    Desalination performance of TFC-PA NF membranes. (a) Variation of permeance and rejection of TFC-PA NF membrane as a function of NaCl concentration in PIP aqueous solution. (b) Rejection curves of the TFC-PA NF membranes prepared with the addition of 1 wt% NaCl, KCl and LiCl in PIP aqueous solution, respectively, to PEG with different molecular weights and corresponding pore size distributions (inset). (c) Permeance and corresponding rejection of the membrane prepared with the addition of 1 wt% NaCl in PIP aqueous solution to various salts as feed solutions (the concentrations of these feeds are all 1000 ppm). (d) Summary of the desalination performance of the state-of-the-art NF membranes reported previously and the membranes obtained in this work while using Na2SO4 solution as feed. The literatures cited in Fig. 4d (Ref. S1–S17) are listed in Supplementary information.

  • Figure 5

    Characterization of the hydration state of BCN nanofilm. (a) Experimental scheme showing the test of SFG vibrational spectroscopy on BCN nanofilm. (b) SFG spectra of the BCN nanofilm in air, prewetted by pure water, and water containing NaCl with concentrations of 0.5 wt%,1 wt%, and 2 wt%. (c) Snapshot of the simulation system composed by BCN nanofilm (signed as green), water molecules (signed as yellow spheres) and Na+ ions (signed as blue spheres) after 20 ns simulation. (d) Enlarged MD simulated distribution of water molecules and Na+ ions around BCNs. (e) PMF between the BCN nanofilm and water with and without NaCl.


Contact and support